It is known that solid metal nanoparticles (i.e. solid, single metal spheres of uniform composition and nanometer dimensions) possess unique optical properties. In particular, metal nanoparticles (especially the coinage metals) display a pronounced optical resonance. This so-called plasmon resonance is due to the collective coupling of the conduction electrons in the metal sphere to the incident electromagnetic field. This resonance can be dominated by absorption or scattering depending on the radius of the nanoparticle with respect to the wavelength of the incident electromagnetic radiation. Associated with this plasmon resonance is a strong local field enhancement in the interior of the metal nanoparticle. A variety of potentially useful devices can be fabricated to take advantage of these specific optical properties. For example, optical filters or chemical sensors based on surface enhanced Raman scattering (SERS) have been fabricated.
A serious practical limitation to realizing many applications of solid metal nanoparticles is the inability to position the plasmon resonance at technologically important wavelengths. For example, solid gold nanoparticles of 10 nm in diameter have a plasmon resonance centered at 520 nm. This plasmon resonance cannot be controllably shifted by more than approximately 30 nanometers by varying the particle diameter or the specific embedding medium.
Metal colloids have a variety of useful optical properties including a strong optical absorption and an extremely large and fast third-order nonlinear optical (NLO) polarizability. These optical properties are attributed to the phasic response of electrons in the metallic particles to electromagnetic fields. This collective electron excitation is known as plasmon resonance.
At resonance, dilute metal colloid solutions have the largest electronic NLO susceptibility of known substances. However, the utility of these solutions is limited because their plasmon resonance is confined to relatively narrow wavelength ranges and cannot readily be shifted. For example, silver particles 10 nm in diameter absorb light maximally at approximately 355 nm, while similar sized gold particles absorb maximally at about 520 nm. These absorbance maximums are insensitive to changes in particle size and various dielectric coatings on the particles.
One method of overcoming this problem is to coat small nonconducting particles with these metals. For example, the reduction of Au on Au2S (reduction of chloroauric acid with sodium sulfide) particles has been shown to red shift the gold colloid absorption maximum from 520 nm to between approximately 600 nm and 900 nm, depending on the amount of gold deposited on the Au2S core and the size of the core. Zhou, et al. (1994). The ratio of the core radius to shell thickness can be controlled by changing the reactant concentrations, or by stopping the reaction. In this case, the diameter of the particle core is directly proportional to the red shift in the wavelength of light that induces gold plasmon resonance. However, gold-sulfide particle diameters are limited to sizes of approximately 40-45 nm with a thin gold shell (less than 5 nm). The limited size of the gold-sulfide particles of Zhou et al. limits the absorbance maximum to wavelengths no larger than 900 nm. See, also Averitt et al. (1997)
An additional limitation of such particles as defined by Zhou et al. is that both the core and the shell are grown as a result of a single chemical reaction, thus limiting the choice of the core material and the shell material to Au2S and Au respectively. In addition, only the ratio of the core radius to shell thickness may be controlled; independent control of the core radius and the shell thickness is not possible.
Neideljkovic and Patel (1991) disclosed silver-coated silver bromide particles that are produced by intense UV irradiation of a mixture of silver bromide, silver, sodium dodecylsulfate (SDS) and ethylenediamine tetraacetic acid (EDTA). The Neideljkovic particles range in size from approximately 10 to 40 nm and are irregularly-shaped, as determined by transmission electron micrography. Predictably, the spectra obtained from these particle preparations are extremely broad.
In U.S. Pat. No. 5,023,139, Birnboim et al. disclosed theoretical calculations indicating that metal-coated, semi-conducting, nanometer-sized particles containing should exhibit third-order nonlinear optical susceptibility relative to uncoated dielectric nanoparticles (due to local field enhancement). Their static calculations were based on hypothetical compositions. The preferred embodiments disclosed by Birnboim et al. are, in fact, not particles with metallic shells on their surfaces. In those embodiments theoretically proposed by Birnboim et al. that do in fact propose a metal outer shell, there is an additional requirement as to the specific medium in which they must be used in order to properly function.
However, Birnboim does not disclose methods for preparing the disclosed hypothetical compositions. Furthermore, Birnboim""s calculations do not take into account surface electron scattering. Surface electron scattering strongly modifies the optical response of all metallic structures that possess at least one dimension smaller than the bulk electron mean free path (e.g. in Au at room temperature the bulk electron mean free path is about 40 nm). This effect reduces the local field enhancement factor that in turn reduces the resonant third order nonlinear optical susceptibility associated with the nanoshell geometry. See, Averitt et al. (1997). Since typical shell thicknesses for these compositions fall below 40 nm, Birnboim et al""s theoretical calculations fail to account for this effect which is an important aspect of the optical response for functional metal nanoshells. Finally, it is important to realize that the hypothetical metal nanoshells of Birnboim pertains specifically to the enhancement of the third order nonlinear optical susceptibility.
Moreover, Birnboim-type particles are by definition particles much smaller than a wavelength of light (less than 0.10 times a given wavelength of light), and are particles in which the dielectric property of the nanoshell (in those instances where it is in fact a metal shell that is used in Birnboim et al.) are defined as the bulk dielectric property of the metal selected. In practice, this requires these smaller-than-a-wavelength particles to have metal shell layer thicknesses of many nanometers (e.g., for Au, such minute particles meeting the theoretical requirements of the Birnboim calculations and the bulk dielectric properties of Au required thereby, would necessarily have shells at least 40 nm in thickness). The physical limitations placed on the construction of such particles is therefore considerable.
Methods and materials are needed that can be used to shift the wavelength of maximum absorption of metal colloids. Methods for producing materials having defined wavelength absorbance maxima across the visible and infrared range of the electromagnetic spectrum are needed. Particularly, such metal nanoshell composites should be constructed in a manner to allow a choice of core material, core dimensions, and core geometry independent of those criteria for the shell material. Compositions produced by these methods should have relatively homogeneous structures and should not have to rely on suspension in a particular medium in order to exhibit their desired absorption characteristics. Moreover, materials and methods are needed that are not limited in the radial dimensions of the shell layer by the bulk dielectric properties of the metal selected, and are not limited in size to much smaller than a wavelength of light. Materials impregnated with these compositions could be used in such diverse applications as optical switching devices, optical communication systems, infrared detectors, infrared cloaking devices, passive solar radiation collection or deflecting devices and the like.
The present invention relates to compositions and methods for synthesizing unique composite particles having homogeneous structures and defined wavelength absorbance maxima. The present compositions consist of a nonconducting inner layer that is surrounded by a layer made of a conducting material. Also contemplated are unique methods for making the present compositions such that the resulting compositions can be tuned to absorb electromagnetic radiation maximally at wavelengths in the visible or infrared regions of the electromagnetic spectrum.
Particularly, the metal nanoshells of the present invention are not restricted to a single core or single shell material; permutations of materials are made possible by the novel methodology disclosed here for the first time to make such metal nanoshells. There is no requirement to use the metal nanoshells of the present invention in any given medium in order for them to exhibit their absorptive qualities; in fact, it is anticipated that such metal nanoshells may find particular utility as surface treatments and coatings totally absent any surrounding medium. Because the core and shell material is selected independently, any number of such permutations is made possible. The particles of the invention are also relatively uniform in size and shape by virtue of the methods of the invention used to construct them. Most importantly, while the metal nanoshells of the present invention may be much smaller than a wavelength of light, they are not limited in the thickness of their metal shells to account for the bulk dielectric properties of the metal comprising the shell. In fact, due to the one-atom-or-molecule-at-a-time approach to building the metal shell disclosed by the present inventors, the thickness of the metal shell may be controlled from as low as atomic thicknesses.
The spectral location of the maximum of the plasmon resonance peak for this geometry depends sensitively upon the ratio of the core radius to shell thickness, as well as the dielectric functions of the core and shell. The presence of a dielectric core shifts the plasmon resonance to longer wavelengths relative to a solid nanoparticle made exclusively of the metallic shell material. For a given core radius, a thin shell will have a plasmon peak that is shifted to longer wavelengths relative to a thicker shell. It is to be emphasized that metal nanoshells possess all of the same technologically viable optical properties as solid metal nanoparticles in addition to this extremely important aspect of resonance tunability.
This invention relates in certain regards to a general method for the production of nanoshell composites. In particular, the choice of the core material and geometry can be determined independently of the shell material. Similarly, the choice of the shell material and shell thickness is independent of the desired core material. It is also important to note that the coating methods and materials described herein will allow for the fabrication of other unique geometries with potentially unique properties; the utility of this method extends far beyond the fabrication of spherical nanoshells. For example, coated cubes or pyramids or cylinders, planar surfaces, or structures patterned onto or etched into a planar surface, to name a few, can be easily fabricated using the same methods detailed herein.
The present embodiments have wavelength absorbance maxima in the range of approximately 400 nm to 20 xcexcm. The low wavelength end of the range is defined by the natural plasmon resonance of the metal-like conductor in a shell layer. For any given particle, the maximum absorbance depends upon the ratio of the thickness of the nonconducting layer to the conducting shell layer. Shown in FIG. 1 are absorption maxima for particles having core to shell ratios of 60:20, 60:10, 60:7, and 60:5. As shown, these particles have absorbance peaks of approximately 740, 830, 910, and 1010, nanometers respectively.
The specially tailored particles or particle mixtures of the invention can be added to polymers during their preparation by methods well known in the art. Suitable polymers include polyethylene, polyvinyl alcohol (PVA), latex, nylon, teflon, acrylic, kevlar, epoxy, glasses and the like. Solubility of nanoparticles into polymers can be facilitated by functionalization of the nanoparticle surfaces with suitable molecules known to those of skill in the art. The resulting coatings and materials can absorb radiation over the wavelength region of the incorporated particles. Embodiments containing these materials can be used in thermal management to produce more energy efficient buildings, automobiles and storage chambers creating savings in air conditioning and heating costs. Fullerene and/or polymer thin film chemistry could be used to incorporate the present materials into photovoltaic devices by methods known in that art. This approach extends the spectral response of solar cells across the infrared region of the solar emission spectrum, providing more efficient solar cells. Similarly, solar cells or similar devices operated in a photoconductive rather than photovoltaic mode could be used to provide new low-cost, compact infrared detectors useful for a range of applications, including but not limited to environmental emissions testing, medical imaging or night vision surveillance.
The compositions of the present invention are particles that have at least two layers. At least one layer is immediately adjacent to and surrounds another layer. The innermost layer is said to be a core. A layer that surrounds the core is said to be a shell layer. The shell layer is metal-like in that it can conduct electricity and is made of a metal or metal-like material. It is preferred that at least one shell layer readily conduct electricity, however, the invention only requires that one shell layer have a lower dielectric constant than the adjacent inner layer. In some embodiments, this metal or metal-like shell layer is the outermost layer. In other embodiments, the shell layer immediately adjacent the core is not the outer most shell layer. Additional layers, such as a non-conducting layer, a conducting layer, or a sequence of such layers, such as an alternating sequence of non-conducting and conducting layers, may be bound to this shell layer using the methods described herein and using materials and methods known well to those of skill in the relevant art. Thus, for the purposes of this invention the term conductor is defined by reference to the adjacent inner layer and includes any material having a lower dielectric constant than its immediately adjacent inner layer.
It is also preferred that the adjacent inner layer to the shell layer be nonconducting. Specifically contemplated are nonconducting layers made of dielectric materials and semiconductors. Suitable dielectric materials include but are not limited to silicon dioxide, titanium dioxide, polymethyl methacrylate (PMMA), polystyrene, gold sulfide and macromolecules such as dendrimers. In certain embodiments of this invention, the nonconducting layer is comprised of a semiconductor material. For example, core particles may be made of CdSe, CdS or GaAs. The material of the nonconducting layer influences the properties of the particle. For example, if the dielectric constant of the shell layer is larger relative to a particle having a core with a given dielectric constant, the absorbance maximum of the particle will be blue-shifted relative to a particle having a core with a lower dielectric constant. The core may also be a combination or a layered combination of dielectric materials such as those listed above.
One layer of a particle is its core as noted above. In a two layer particle, the core is a nonconducting layer. The preferred core is a monodisperse, spherical particle that is easily synthesized in a wide range of sizes, and has a surface that can be chemically derivatized. It is also preferred that cores be made of dielectric materials or semiconductors.
Although in preferred embodiments the core is spherical in shape, the core may have other shapes such as cubical, cylindrical or hemispherical. Regardless of the geometry of the core, it is preferred that the particles be homogenous in size and shape in preferred embodiments. In other embodiments, mixtures are purposefully constructed wherein there is a controlled size and shape distribution. In spherical embodiments, particles have a homogeneous radius that can range from approximately 1 to 10 nanometers to several microns depending upon the desired absorbance maximum of the embodiment. For the purposes of this invention, homogeneity exists when over about 99% of the particles do not vary in diameter by more than 100%. Under this definition a particle preparation wherein 99% of the particles have diameters between about 50 nm to 100 nm would be said to be homogeneous. Specific applications, however, as discussed in the examples, may rely on mixtures of metal nanoshells with different core and shell sizes.
Monodisperse colloidal silica is the preferred nonconducting layer or core material. These particles can be produced by the base catalyzed reaction of tetraalkoxysilanes, by techniques known well to those of skill in the art. Nearly spherical silica cores having sizes ranging from 10 nm to greater than 4 xcexcm with a variation in particle diameter of only a few percent are preferred.
In the present embodiments, at least one nonconducting layer is surrounded by a layer that is made of a conducting material. Generally, the conducting layer is metallic but it may also be an organic conducting material such as polyacetylene, doped polyanaline and the like. Suitable metals include the noble and coinage metals but any metal that can conduct electricity is suitable. Metals that are particularly well suited for use in shells include but are not limited to gold, silver, copper, platinum, palladium, lead, iron or the like. Gold and silver are preferred. Alloys or non-homogenous mixtures of such metals may also be used.
The conducting shell layers of the present invention have thicknesses that range from approximately 1 to 100 nm. They may coat the adjacent inner layer fully and uniformly or may partially coat that layer with atomic or molecular clusters. In either embodiment, at least approximately 30% of the adjacent inner layer is coated by the conducting layer.
In certain embodiments, the shell layer is linked to the dielectric core layer through a linker molecule. Suitable linker molecules include any molecule that is capable of binding both the core and atoms, ions or molecules of the shell. Preferably, linker binding is covalent to both the shell and the inner layer but binding may also be through ionic bonds, lone-pair interactions, hydrogen bonds, Van der Waals interaction or the like. In certain embodiments, the linker binds existing metallic clusters to the surface of a non-conducting layer. In other embodiments, the linker binds atoms, ions or molecules directly to the surface of a non-conducting layer. Thus, in embodiments that have a core made of CdSe, a suitable linker would be able to bind the CdSe core and molecules in the shell. In preferred embodiments, the silicone dioxide core and gold metallic shell, are linked by aminopropyltriethoxy silane (xe2x80x9cAPTESxe2x80x9d).
The present invention also contemplates unique chemical methods for producing the disclosed compositions in solution. Generally, assembly occurs by way of the following steps. First, core particles are grown or otherwise obtained. Next, a linker molecule is bound to the core. Then, clusters of molecules that comprise the conducting shell layer are reacted with a free reactive end on the linker molecules. These clusters may complete the shell layer or form nucleation sites for the growth of a complete shell layer around the core.
The conditions under which each of the synthetic reactions is carried out determines the overall size and makeup of the particle. For example, in the synthesis of metal shells, reactants include certain concentrations of metal and reducing equivalents that can be altered along with reaction times to vary the shell thickness and morphology. With certain shell materials, the progress of this reaction can be followed spectrophotometrically due to the distinct absorption peaks of the particles in the visible and infrared regions of the electromagnetic spectrum.
One method for obtaining core particles is by the synthetic method described in Example II, which can be used to synthesize particles of silicon dioxide. Alternatively, in some cases suitable core particles may be purchased. For example, silicone dioxide core particles such as LUDOX TM-50 colloidal silica are available from Aldrich Chemical Co., Milwaukee, Wis.
One unique aspect of the present method is the attachment of conducting materials of the shell to the nonconducting inner layer. In the methods of the invention, this step is carried out in solution. In this method, linker molecules that are capable of chemically linking the conducting layer to the core are first bound to the core. One method of attachment, described in Example III, is for the reaction of APTES with silicon dioxide particles. Other suitable linker molecules include but are not limited to mercaptopropyltrimethoxy silane, 4-aminobutyldimethoxysilane, and the like. One of skill in the art will readily appreciate that the suitability of a linker molecule depends upon the particular embodiment including the composition of the core and of the conducting shell that will eventually surround the core. With this knowledge, one of skill can identify suitable linkers and bind them to core particles or nonconducting inner layers and then react suitable conducting molecular clusters, ions, or atoms of a suitable conducting material to them.
As one of skill in the art can readily appreciate, suitable solvents for linker molecule attachment depend upon the reactants and a variety of solvents may work under a given set of conditions. In Example III, the solvent of choice for the attachment of APTES to silicon dioxide is anhydrous ethanol. Generally, where linkers are attached in condensation reactions, the preferred solvents are anhydrous because such solvents tend to drive the reactions to produce more of the desired final reacted product. One of skill in the art would be able to select a suitable solvent based on chemical methodologies well known in the chemical arts.
Once the linker molecules are bound to the core, a free reactive moiety on the linker is reacted with clusters of molecules, ions or atoms to produce all or part of a conducting shell. In certain embodiments, the clusters are metal atoms. When the clusters are metallic, one suitable attachment method is disclosed in Example IV. Metal clusters, ions or atoms that are linked to the core particle through a linker molecule are said to be xe2x80x9ctethered.xe2x80x9d In certain embodiments the tethered metal atoms or clusters serve as nucleation sites for the deposition of additional metal from solution. In other embodiments, the attachment of metal clusters completes the synthesis.
Methods for the growth of a complete metallic shell on tethered metal clusters are disclosed in Example V. Generally, metal is deposited onto the tethered clusters and enlarges the clusters until a coherent metal shell of the desired thickness is formed. In the method of Example V, the metal can be deposited through reduction process of solution metal onto the tethered clusters. Alternatively, metal can be deposited on the tethered metal clusters by a xe2x80x9ccolloid-basedxe2x80x9d deposition process. The deposition can also be initiated or driven photochemically. The technique of depositing metal onto metal nucleation sites tethered to nonconducting core materials in solution is one of the novel features of the present methods.
In certain preferred embodiments, the metallic shell is the terminal layer. However, attachment of molecules or additional layers can change the physical properties of the particle. A chemical or charge-transfer interaction between the metallic shell and an additional layer, or just the local embedding medium, influences the optical absorption of the particles, as discussed by Kreibig et al, incorporated herein by reference to the extent it provides such methods.
In addition, the near field of the metallic shell can affect the properties of molecules adsorbed on the surface of the nanoparticles. This could be of use in chemical sensing applications. In other embodiments, a non-conducting layer surrounding the metallic layer can provide a steric barrier that is useful when processing or organizing the particles into a particular arrangement. Chemical functionalization of the metal surface is also useful for transferring the metal nanoshells between different solvents, as discussed by Sarathy et al., incorporated herein by reference to the extent it provides such methods. Chemical functionalization may also assist or enable the formation of arrays or crystals of these particles, which will possess additional unique optical properties relating to the periodicity of the array or crystal structure, in similarity with photonic band gap crystals and arrays.
By varying the conditions of the metal deposition reaction, the ratio of the thickness of the metal shell to the nonconducting inner layer can be varied in a predictable and controlled way. Particles can be constructed with metallic shell layer to core layer radius with ratios from 10 to 10xe2x88x923. This large ratio range coupled with control over the core size results in a particle that has a large, frequency-agile absorbance over most of the visible and infrared regions of the spectrum. A theoretical calculation of the plasmon resonance as a function of core/shell ratio is shown in FIG. 2.
There are many possible applications of metal-coated nanoparticles that could utilize the tunability of the plasmon resonance. Nanoshells could be made to absorb or scatter light at specific wavelengths in the visible or infrared range. Such compositions would be ideal for use in a wide range of materials including energy efficient paints, windows, coatings, or fabrics that could be used on or in vehicles and building structures. These compositions could be suspended as an active agent in inks, for cryptographic marking purposes. These materials would also be particularly well suited for use in air heating units or in solar collector materials. Such a solar absorber could also be used as a shield or screen that absorbs or scatters incident solar radiation, keeping the structure cooler than if it were directly exposed to the solar radiation.
Such materials could be useful in many other applications to efficiently xe2x80x9cmanagexe2x80x9d the radiation from any thermal source. For example, these compositions could be adsorbed onto or embedded into materials, thin films, coatings, or fabrics that convert radiation directly into heat (passive solar energy harvesting), or into devices or device components, that convert radiation into electricity via photovoltaic or photoconductive effects, or that convert radiation into chemical energy (fuel cells). Mixtures of these compositions could be made to absorb or scatter solar energy across the entire solar radiation spectrum.
These nanoparticles could be used to sensitize existing photovoltaic, photoconductive, or bolometric devices for enhanced photoresponse and efficiency, and could be used as the functional basis for new device designs. The strong infrared photoresponse of these compositions may be useful for sensitization of many different types of semiconductor or polymer surfaces or films for other applications.
For example, the selective infrared absorption may be useful for laser eye protection, or eye protection from other potentially damaging sources of infrared radiation. The enhanced optical field in the vicinity (1-20 nm) of a nanoparticle may facilitate photochemistry or photoelectrochemistry, either on a nanoparticle surface, on a substrate upon which a nanoparticle is attached, or an electrode upon which the nanoparticle is attached or embedded. Structures containing such compositions could be used in photoconductive applications such as in infrared detectors. Infrared detectors utilizing the properties of these compositions could be used in a wide range of applications such as detecting emissions in environmental monitoring, optical telecommunications networks, wavelength selective, mid-infrared detectors for medical imaging, night vision surveillance equipment or infrared telescopes.
Compositions constructed with different resonant frequencies could be selectively manipulated, levitated, or xe2x80x9csiftedxe2x80x9d using the wavelength dependent dipole force of a laser beam or beams. Additionally, metal nanoshells can be made that possess unique electronic properties that could be useful in specific electronic device applications. The fabrication of homogeneous metal shells comprised of several hundred or a few thousand atoms covering dielectric cores as small as 1 nm would have well-defined electronic energy levels, similar to molecules, whose energy level spacings are controllably defined by the nanoshell geometry as described by Puska and Neiminen, incorporated herein by reference to the extent it provides such methods.
In other words, the energy eigenstates of very small diameter metal nanoshells are defined not only by the shell thickness, but by the diameter of the inner core as well. For small core diameters, both the optical and electronic properties are unique to the ultra small core/shell structure. Such metal nanoshells might find application in nanoscale devices, such as single electron transistors or coulomb blockade devices that rely on having well defined electronic energy level spacings. They may also provide useful electronic or electrical properties as components of larger devices. In addition, there could be higher energy optical resonances of metal nanoshells that lie in the vacuum ultraviolet or x-ray region of the electromagnetic spectrum, a property that could be applied to the fabrication of x-ray absorbers or detectors.
The enhanced polarizability at the plasmon resonance of these compositions could be used in chemical sensing or chemical analysis applications, where information concerning the properties of molecules adsorbed onto the nanoparticle surface is obtained. Such compositions may permit the use of surface enhanced raman scattering (SERS) to be performed upon adsorbate or adjacent molecules using laser wavelengths in the near-infrared or infrared region of the spectrum. For compositions prepared where the shell is incomplete, second-order nonlinear optical effects may be enhanced when such oriented compositions are adsorbed onto a surface or embedded into an appropriate medium.